화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Korean Journal of Chemical Engineering, Vol.36, No.6, 981-987, June, 2019
DOI10.1007/s11814-019-0279-x  Export Citation
High strength Cu foil without self-annealing prepared by 2M5S-PEG-SPS
Anna Lee, Myung Jun Kim1, Seunghoe Choe2, and Jae Jeong Kim†
  • School of Chemical and Biological Engineering, Institute of Chemical Process, Seoul National University, 599 Gwanangno, Gwanak-gu, Seoul 08826, Korea
  • 1Department of Chemistry, Duke University, 124 Science Drive, Box 90354, Durham, North Carolina 27708, United States, USA
  • 2Electrochemistry Department, Surface Technology Division, Korea Institute of Materials Science (KIMS), 797 Changwondaero, Sungsan-gu, Changwon, Gyeongnam 51508, Korea
E-mail:
Cu foil has widely been used as a current collector for Li ion batteries due to its excellent electrical, mechanical properties and facile fabrication process, but improvement in the properties of Cu foil is necessary for continuous development of the Li ion battery. Thinner and stronger Cu foil is being demanded, and the self-annealing of Cu foil needs to be prevented for effective control of properties as well as higher productivity of the fabrication process. We investigated the effects of three additives, 2-mercapto-5-benzimidazole sulfonic acid (2M5S), polyethylene glycol (PEG), and bis (3-sulfopropyl) disulfide (SPS), on the mechanical properties and self-annealing phenomenon of Cu foil. Cu foil deposited with PEG shows the highest tensile strength and elongation after electrodeposition; however, it experiences severe self-annealing for 48 hrs. On the contrary, 2M5S and SPS reduce the self-annealing phenomenon with their incorporation into Cu film, while the initial mechanical properties are worse than those with PEG. Therefore, combinations of additives are investigated to obtain both higher mechanical properties and excellent resistance against self-annealing. Finally, 10 μm-thick Cu foil having a tensile strength of 673MPa and an elongation of 2.9% without self-annealing can be fabricated using PEG-2M5S-SPS.
Keywords:Cu Electrodeposition;Cu Foil;Organic Additive;Mechanical Property;Self-annealing
  1. Scrosati B, Garche J, J. Power Sources, 195(9), 2419 (2010)
  2. Etacheri V, Marom R, Elazari R, Salitra G, Aurbach D, Energy Environ. Sci., 4, 3243 (2011)
  3. Lu LG, Han XB, Li JQ, Hua JF, Ouyang MG, J. Power Sources, 226, 272 (2013)
  4. Kang SW, Xie HM, Zhang WM, Zhang JP, Ma Z, Wang RS, Wua XL, Electrochim. Acta, 176, 604 (2015)
  5. Kubo T, Fujishima K, Yamamoto N, U.S. Patent, 5,326,455 (1994).
  6. Takahashi N, Hirasawa Y, U.S. Patent, 20,020,015,833 (2001).
  7. Lin CC, Yen CH, Lin SC, Hu CC, Dow WP, J. Electrochem. Soc., 164(13), D810 (2017)
  8. Cho SK, Kim MJ, Koo HC, Kwon OJ, Kim JJ, Thin Solid Films, 520(6), 2136 (2012)
  9. Kim HC, Kim MJ, Choe S, Lim T, Park KJ, Kim KH, Ahn SH, Kim SK, Kim JJ, J. Electrochem. Soc., 161(14), D749 (2014)
  10. Kim HC, Kim MJ, Lim T, Park KJ, Kim KH, Choe S, Kim SK, Kim JJ, Thin Solid Films, 550, 421 (2014)
  11. Chan PF, Ren RH, Wen SI, Chang HC, Dow WP, J. Electrochem. Soc., 164(9), D660 (2017)
  12. Hakamada M, Nakamoto Y, Matsumoto H, Iwasaki H, Chen Y, Kusuda H, Mabuchi M, Mater. Sci. Eng. A-Struct. Mater. Prop. Microstruct. Process., 457, 120 (2007)
  13. Xu D, Kwan WL, Chen K, Zhang X, Ozolins V, Tu KN, Appl. Phys. Lett., 91, 254105 (2007)
  14. Lu L, Shen Y, Chen X, Qian L, Lu K, Science, 304, 422 (2004)
  15. Lu L, Chen X, Huang X, Lu K, Science, 323, 607 (2009)
  16. Lu K, Lu L, Suresh S, Science, 324, 349 (2009)
  17. Kim MJ, Cho SK, Koo HC, Lim T, Park KJ, Kim JJ, J. Electrochem. Soc., 157(11), D564 (2010)
  18. Kim MJ, Lim T, Park KJ, Cho SK, Kim SK, Kim JJ, J. Electrochem. Soc., 159(9), D538 (2012)
  19. Kim MJ, Lim T, Park KJ, Kwon OJ, Kim SK, Kim JJ, J. Electrochem. Soc., 159(9), D544 (2012)
  20. Chen X, Lu L, Scrip. Mater., 57, 133 (2007)
  21. Lui GT, Chen D, Kuo JC, J. Phys. D-Appl. Phys., 42, 215410 (2009)
  22. Vas’Ko VA, Tabakovic I, Riemer SC, Kief MT, Microelectron. Eng., 75, 71 (2004)
  23. Stoychev DS, Tomov IV, Vitanova IB, J. Appl. Electrochem., 15, 879 (1985)
  24. Mizumoto S, Nawafune H, Hiroo T, Haga M, J. Surf. Finish. Soc. Jpn., 44, 687 (1993)
  25. Nawafune H, Fukuda Y, Mizumoto S, Haga M, J. Surf. Finish. Soc. Jpn., 46, 834 (1995)
  26. Harper JME, Cabral C, Andricacos PC, Gignac L, Noyan IC, Rodbell KP, Hu CK, J. Appl. Phys., 86, 2516 (1999)
  27. Vas'ko VA, Tabakovic I, Riemer SC, Electrochem. Solid State Lett., 6(7), C100 (2003)
  28. Lee CH, Park CO, Jpn. J. Appl. Phys., 42, 4484 (2003)
  29. Stangl M, Acker J, Dittel V, Gruner W, Hoffmann V, Wetzig K, Microelectron. Eng., 82, 189 (2005)
  30. Shinada E, Nagoshi T, Chang TFM, Sone M, Mater. Sci. Semicond. Process, 16, 633 (2013)
  31. Ho CE, Chen CC, Lu MK, Lee YW, Wu YS, Surf. Coat. Technol., 303, 86 (2016)
  32. Chen CC, Yang CH, Wu YS, Ho C E, Surf. Coat. Technol., 320, 489 (2017)
  33. Matsuda M, Takahashi T, Yoshihara S, Dobashi M, Trans. Jap. Electron. Packaging, 2, 55 (2009)
  34. Cheng MY, Chen KW, Liu TF, Wang YL, Feng HP, Thin Solid Films, 518(24), 7468 (2010)
  35. Stangl M, Militzer M, J. Appl. Phys., 103, 113521 (2008)
  36. Hasegawa M, Nonaka Y, Negishi Y, Okinaka Y, Osaka T, J. Electrochem. Soc., 153(2), C117 (2006)
  37. Osaka T, Yamachika N, Yoshino M, Hasegawa M, Negishi Y, Okinaka Y, Electrochem. Solid State Lett., 12(3), D15 (2009)
  38. Nakahara S, Ahmed S, Buckley DN, Electrochem. Solid State Lett., 10(2), D17 (2007)
  39. Surholt T, Herzig C, Acta Mater., 45, 3817 (1997)
  40. Hansen N, Ralph B, Acta Metall., 30, 411 (1982)
  41. Flinn JE, Field DP, Korth GE, Lillo TM, Macheret J, Acta Mater., 49, 2065 (2001)
  42. Hutchinson JW, Proc. Roy. Soc. Lond. A., 319, 247 (1970)
  43. Kiser MT, Zok FW, Wilkinson DS, Acta Mater., 44, 3465 (1996)
  44. Nan CW, Clarke DR, Acta Mater., 44, 3801 (1996)
  45. Nan CW, Birringer R, Gleiter H, Scrip. Mater., 37, 969 (1997)
  46. Peng L, Liu F, Ni J, Lai X, Mater. Des., 28, 1731 (2007)